Adhesion promoting agents

ABSTRACT

DISCLOSED ARE NITROGEN CONTAINING SILANE COMPOUNDS OF THE FORMULA   (X)A-SI(-T)B-(R-(Z)E)D   WHERE R IS AN ORGANIC RADICAL, X IS SELECTED FROM HALO, HYDROXY, ALKOXY, ARYLOXY, ORGANO OXYCARBONYL, AZIDO, AMINE, AND AMIDE RADICALS; T IS SELECTED FROM ALKYL, CYCLOALKYL, ARYL, ALKARYL, AND ARALKYL RADICALS; A IS AN INTEGER FROM 1 TO 3; B IS AN INTEGER FROM 0 TO 2; C IS AN INTEGER FROM 1 TO 10; D IS AN INTEGER FROM 1 TO 3; AND A+B+D EQUALS4; AND Z ES SELECTED FROM   -OOC-C(-R&#39;&#39;)-N3, -OOC-N3, AND -SO2-N3   WHERE R&#39;&#39; IS SELECTED FROM HYDROGEN, ALKYL, CYCLOALKYL, ARYL AND -COOR&#34; RADICALS; WHRE R&#34; IS SELECTED FROM ALKYL, CYCLOALKYL, AND ARYL RADICALS. ALSO DISCLOSED IS A PROCESS TO PROMOTE THE ADHESION OF PLYMERS TO SLICEOUS MATERIALS, METALS, METAL OXIDES, AND OTHER POLYMERS USING THE SAID SILANE COMPOUNDS. IN PARTICULAR, THERE IS DISCLOSED A PROCESS OF IMPROVING THE ADHESION OF TIRE CORD TO RUBBER TIRE STOCK USING THE SAID SILANE COMPOUNDS. THE CROSS-LINKING OF POLYMERS WITH THE SILANE COMPOUNDSIS ALSO DISCLOSED.

United States Patent Ofiice 3,706,592 Patented Dec. 19, 1972 3,706,592ADHESION PROMOTING AGENTS J. Brent Thomson, Wilmington, Del., assignorto Hercules Incorporated, Wilmington, Del.

No Drawing. Application Sept. 30, 1969, Ser. No. 862,531,

which is a continuation-in-part of abandoned application Ser. No.789,974, Dec. 31, 1968. Divided and this application July 30, 1971, Ser.No. 167,799

Int. Cl. C03c 25/02, 17/30; 1332b 17/04 US. Cl. 117-72 18 ClaimsABSTRACT OF THE DISCLOSURE Disclosed are nitrogen containing silanecompounds of the formula where R is an organic radical, X is selectedfrom halo, hydroxy, alkoxy, aryloxy, organo oxycarbonyl, azido, amine,and amide radicals; T is selected from alkyl, cycloalkyl, aryl, alkaryl,and aralkyl radicals; a is an integer from 1 to 3; b is an integer fromto 2; c is an integer from 1 to d is an integer from 1 to 3; and a+b+dequals 4; and Z is selected from where R is selected from hydrogen,alkyl, cycloalkyl, aryl and COOR" radicals; where R is selected fromalkyl, cycloalkyl, and aryl radicals. Also disclosed is a process topromote the adhesion of polymers to siliceous materials, metals, metaloxides, and other polymers using the said silane compounds. Inparticular, there is disclosed a process of improving the adhesion oftire cord to rubber tire stock using the said silane compounds. Thecross-linking of polymers with the silane compounds is also disclosed.

This application is a division of my copending United States applicationSer. No. 862,531, filed Sept. 30, 1969, which in turn is acontinuation-in-part of my United States application Ser. No. 789,974,filed Dec. 31, 1968, now abandoned.

This invention relates to a method of improving the adhesion of polymersto siliceous materials, metals, metal oxides and in adhering one polymerto another by use of the new organic compounds and to the products soproduced.

It is known in the art to coat various substrates with polymers.However, in many cases the bond between the polymer and the substrate isweak. In still other cases the adhesion is almost completely lost whenthe polymer coated article is subjected to moist conditions.

It has now been found that the adhesion of any polymer to siliceousmaterials, metals, metal oxides or other polymer substrates can begreatly improved by the treatment of the substrate with a nitrogencontaining silane compound having the general formula )aSi Z cin where Ris an organic radical; X is selected from halo, hydroxy, alkoxy,aryloxy, organo oxycarbonyl, azido, amine, and amide radicals; T isselected from alkyl, cycloalkyl, aryl, alkaryl, and aralkyl radicals; ais an integer from 1 to 3; b is an integer from 0 to 2; c is an integerfrom 1 to 10; d is an integer from 1 to 3; and a+b+d equals 4; and Z isselected from where R is selected from hydrogen, alkyl, cycloalkyl,aryl, and -COOR radicals; where R" is selected from alkyl, cycloalkyland aryl radicals. Not only does the treatment in accordance with thisinvention increase the adhesion of the polymer to the substrate, it alsogreatly improves wet strength retention.

Any polymer can be bonded to a siliceous material, metal, metal oxideor-another polymer with said silane compound in accordance with thisinvention. Exemplary of the polymers which can be so bonded are thehydrocarbon polymers including saturated, unsaturated, linear, atactic,crystalline or nonlinear amorphous polymers, c0- polymers, terpolymers,etc. as for example polyethylene, polypropylene,poly(4-methylpentene-l), polybutene 1, polystyrene, styrene-butadienerubber, butyl rubber, natural rubber, polybutadiene, polyisobutylene,ethylenepropylene copolymer, cis-1,4-polyisoprene,ethylene-propylene-dicyclopentadiene terpolymer, etc. and blends ofthese polymers with each other. In addition, nonhydrocarbon polymersincluding the cellulose esters such as cellulose acetate butyrate',acetate rayon, cellulose partial alkyl ethers such as hydroxyethyl andhydroxypropyl cellulose; viscose rayon; polyesters such as poly(ethyleneterephthalate), drying and nondrying alkyd resins, etc.; poly(alkyleneoxides) such as poly(ethylene oxide) and poly(propylene oxide), etc.;poly(arylene oxides) such as poly(phenylene oxide, etc.; the polyam idessuch as nylon, perlon-L, etc.; and poly(vinyl alkyl ethers) such aspoly(vinyl methyl ether), etc.; vinyl chloride polymers containing atleast 10 mole percent of vinyl chloride such as poly(vinyl chloride),vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinylidenechloride copolymers, vinyl chloride-maleic anhydride copolymers, vinylch10 ride-fumaric acid copolymers, vinyl chloride-vinyl 'acetalcopolymers such as the vinyl chloride-vinyl butyral copolymers, vinylchloride-vinylidene chloride-acrylonitrile terpolymers, vinylchloride-vinyl acetate-maleic anhydride terpolymers etc.; chlorinatednatural rubber; ethylenevinyl acetate copolymers; poly(vinylidenechloride); vinylidene chloride-acrylonitrile copolymers; poly(ethylacrylate); poly(ethyl methacrylate); polysulfone; epoxy resins; poly[3,3bis(chloromethyl)oxetane]; polychloroprene; butadiene acrylonitrilecopolymers: butadieneacrylonitrile-styrene terpolymers; etc. can bebonded to the above-mentioned materials.

The materials or substrates to which the polymers may be bonded, asstated above, include siliceous materials such as glass, asbestos, sand,clay, concrete, stone, brick, ceramic materials, etc.; metals such asaluminum, cadmium, chromium, copper, magnesium, nickel, silver, tin,titanium, zinc, etc. and alloys of the metals such as brass, bronze,steel, nickel chrome, etc., and including metals which have been surfacetreated with phosphates, chromates, etc.; metal oxides such as aluminumoxide, iron oixdes, lead oxides, titanium dioxide, zinc oxide, etc.; andother polymers. By the term other polymers is meant any polymer otherthan the polymer which is to be bonded. These materials to which thepolymers may be bonded can be in various forms such as sheets, plates,blocks, wires, cloth, fibers, particles, powders, etc. For example, inaccordance with this invention a polymer can be bonded to glass fibers,cord, plates, or cloth, asbestos sheets or fibers, siliceous fillerssuch as silicon dioxide (sand) or clay, metal sheets, plates or wires,metal oxide pigments, polymer sheets, woven fabric fibers, etc.

The process of this invention can be carried out in various ways. Forexample the material or substrate can be coated with a solution of thesilane compound and allowed to dry thus inducing bonding through thesilyl group. A polymer can be bonded to the thus treated material at thedecomposition temperature of the azide or diazo group. By another methodthe silane compound and polymer can be deposited together on thematerial and then heated to the decomposition temperature of the azideor diazo group. By still another method a polymer can be treated withthe silane compound so as to react the azide or diazo functional groupunder conditions such that silane condensations do not occur.Subsequently the material or substrate can be contacted with the thustreated polymer so that coupling occurs through the silyl group. Nomatter which method is used it will be necessary, in accordance withthis invention, to heat the silane compound to initiate the bondingreaction through the azide or diazo group. The temperature at whichbonding is effected can be varied over a wide range depending upon thespecific silane compound employed. In general, however, the temperaturewill be in the range of from about 70 C. to about 350 C. Various amountsof silane compound can be used depending upon the specific compound, thesurface area to be covered, the polymer to be bonded to the material,etc. In general the silane compound will be employed in the form of asolution which can be sprayed, brushed, or poured over the surface ofthe material. Alternatively, the material or substrate can be dippedinto a solution or emulsion of the silane compound. These new compoundsare generally soluble in solvents such as methylene chloride,ethylenedichloride, trichloroethylene, perchloroethylene, methanol,ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, benzene,toluene, etc. and will generally be used in concentrations of from about0.01% to about 20.0% more preferably from about 0.05% to about 5.0% byweight.

In one modification of this invention the nitrogen containing silanecompounds can be used to bond various types of reinforcing materials,such as fibers, yarn, cord, fabric, and the like to polymer (rubber)stock. A typical example of bonding reinforcing material is the bondinof poly(ethylene terephthalate) tire cord to rubber tire stock.

The said polyester tire cord is first treated with the silane compound.This can be accomplished by contacting the cord with a nitrogencontaining silane compound as for example, by dipping, spraying,brushing, or running it over a coated roll with a solution or dispersionof the silane compound in a suitable liquid. In the next step the thustreated cord is heated to a temperature sufiicient to decompose theazide or diazo functional group. In so doing, it is believed the azideor diazo group reacts with the polyester leaving the silyl group freefor later reaction. Next, the treated cord may be dipped in a standardindustrial coating (adhesive) which is compatible with the rubber inwhich the cord is to be embedded. The coating is a conventional tirecord adhesive essentially comprising a mixture of a phenol-aldehyderesin and a rubber latex. If desired, the dip in the conventional tirecord adhesive can be omitted with a proportionate decrease inadhesive'strength. Finally, the thus treated tire cord is embedded in acommercial vulcanizable tire stock and cured. While polyester tire cordis recited above, various other synthetic fibers, cords, fabrics, andthe like can be bonded to rubber stock in accordance with thisinvention. Such other reinforcing materials include polyolefin,polyamide, polycarbonate, rayon and glass fibers, cords, fabrics and thelike. In the case of bonding glass reinforcing material to rubber tirestock, the heat treatment following the contacting with a nitrogencontaining silane compound (described above) may not be required becauseit is believed the silyl groups react with the glass leaving the azideor diazo functional groups free for later reaction.

In another modification of this invention, metal objects, such as metalcans can be treated with a solution of the silane compound, coated witha polymer latex or dispersion and then heated to form a tightly bonded,impervious coating. It will be readily apparent to those skilled in theart that the process of this invention lends itself to any occurrencewhere polymers are to be bonded to siliceous materials, metals, metaloxides or other polymers.

In addition to the above modification of this invention, the nitrogencontaining silane compounds can be used to cross-link polymers.Cross-linking can be carried out by merely admixing the polymer with asmall amount of silane compound and any well known basic or acidiccondensation catalyst. Typical of such catalysts are hydrochloric acid,hydrobromic acid, acetic acid, sodium hydroxide, ammonium hydroxide andthe like. In the presence of water and at higher temperaturescross-linking may occur without the addition of a condensation catalyst.In cross-linking it is believed the azide or diazo functional groupsreact with the polymers while the silyl groups condense, thus formingbonds between polymer chains.

The nitrogen containing silane compound of this invention, as statedabove, have the general formula where X, T, R, Z, a, b, c, and d aredefined as above. Generally, R will be selected from the groupconsisting of the hydrocarbon, halo-substituted hydrocarbon,hydrocarbon-oxy-hydrocarbon, hydrocarbon-thio-hydrocarbon andhydrocarbon-sulfonyl-hydrocarbon divalent radicals. In preferredembodiments of this invention R will be a divalent organic radicalselected from the group consisting of alkylene radicals such as thestraight and branched C -C alkylene radicals which include, forinstance, the methylene, ethylene, trimethylene, tetramethylene,pentamethylene, hexamethylene, octamethylene, decamethylene,dodecamethylene, octadecamethylene, etc. radicals; cycloalkyleneradicals such as the C -C cycloalkylene radicals which include, forinstance, the cyclohexylene, cyclopentylene, cyclooctylene,cyclobutylene, etc. radicals; arylene radicals such as 0-, m-, andp-phenylene, naphthylene, biphenylene, etc. radicals; arylene-dialkyleneradicals, such as o-, m-, and p-xylylene diethylene, o-, m-, andp-phenylene diethylene, etc. radicals; alkylene-diarylene radicals suchas methylene bis (o-, mand p-phenylene), ethylene bis(o-, m-, andpphenylene) etc. radicals; cycloalkylene-dialkylene radicals such as,1,2-, 1,3- and l,4-cyclohexane-dimethylene, 1,2- and 1,3-cyclopentanedimethylene, etc. radicals; and the alkylene-oxy-alkylene radicals,arylene-oxy-arylene radicals, alkarylene-oxy-arylene radicals,alkarylene-oxyalkarylene radicals, aralkylene-oxy-alkylene radicals,aralkylene-oxy-aralkylene radicals, etc. as Well as the correspondingthio and sulfonyl radicals, specific examples of which includeethylene-oxyethylene, propylene-oxybutylene, phenylene-oxy-phenylene,methylenephenyleneoxy phenylene-methylene, phenylenemethyleneoxymethylenephenylene, ethylene-thio-ethylene, phenylenethio-phenylene,phenylenemethylene thio methylenephenylene, butylene-sulfonyl-butylene,etc. radicals. It will, of course, be obvious to those skilled in theart that R can contain other functional groups, which are substantiallyinert to the reactions in which these compounds are used, such asesters, sulfonate esters, amides, sulfonamides, urethanes, and the like.In general R can be hydrogen, alkyl, cycloalkyl, aryl or -CO0R radicals.The most preferred alkyl, cycloalkyl and aryl radicals are methyl,ethyl, propyl, butyl, isobutyl, cyclohexyl, cycloheptyl, phenyl, tolyl,etc. The radical R" can be alkyl, cycloalkyl, or aryl with the mostpreferred radicals being methyl, ethyl, propyl, butyl, isobutyl,cyclohexyl, cycloheptyl, phenyl, tolyl, etc. In general X can be hydroxyor any hydrolyzable radical. Typical hydrolyzable radicals are the haloradicals which include, for instance, the fiuoro, chloro, bromo and iodoradicals; the alkoxy radicals including the C -C straight and branchedchain alkoxy radicals such as methoxy, ethoxy, propoxy, butoxy,isobutoxy, octadecyloxy, etc.; the aryloxy radicals such as phenoxy,etc.; the organo oxycarbonyl radicals including the aliphaticoxycarbonyl radicals such as acetoxy, propionyloxy, stearoyloxy, etc.;the cycloaliphatic oxycarbonyl radicals such as cyclohexylcarbonyloxy,etc.; the aromatic oxycarbonyl radicals such as benzoyloxy, xylyloxy,etc.; the azido radical; the amine radical; the substituted amineradicals such as ethylamine, diethylamine, propylamine, etc.; and theamide radicals such as formamide, acetamide, trifiuoroacetamide,'benzamide, etc. Generally T will be a radical selected from the groupconsisting of alkyl, cycloalkyl, aryl, alkaryl, and aralkyl radicalssuch as methyl, ethyl, propyl, isopropyl, butyl, hexyl, cyclohexyl,cycloheptyl, phenyl, tolyl, benzyl, xylyl, etc.

Typical nitrogen containing silane compounds of this invention are 3-(trimethoxysilyl)propyl diazoacetate,

2- (methyldichlorosilyl)ethyl diazoacetate,

p-(trimethoxysilyl)benzyl diazoacetate,

l-[ (3-trimethoxysilylpropyl)carbamoylldecyl diazoacetate,

4-(trimethoxysilyl)butyl a-diazopropionate,

3-(ethyldimethoxysilyl)propyl a-diazo-a-phenylacetate,

3-(trichlorosily1)propyl a-diazoa-carbomethoxyacetate,

2- (trimethoxysilyl) ethyl a-diazo-a-carbophenoxyacetate,

4-(ethoxydichlorosilyl)cyclohexyl diazoacetate,

3- (trimethoxysilyl propyl azidoformate,

3- (methyldimethoxysilyl)propyl azidoformate,

2-chloro-3- 3- (trimethoxysilyl propoxy] propyl azidoformate,

3- (triazidosilyl propyl azidoformate,

2-(trimethoxysilyl)ethyl azidoformate,

3-(triacetoxysilyl)propyl azidoformate,

2- 3- (trimethoxysilyl) propoxy] ethyl azidoformate,

3-(methyldiacetosilyl)propyl azidoformate,

2- (ethyldipropionyloxysilyl)ethyl azidoformate,

p-(trimethoxysilyl)phenyl azidoformate,

4-(diethoxychlorosilyl)butyl azidoformate,

4-(ethyldimethoxysilyl)cyclohexyl azidoformate,

3-(phenyldichlorosilyl)propyl azidoformate,

4- trisdimethylaminosilyl butyl azidoformate,

S-(trimethoxysilyl)amylsulfonyl azide,

4- (trimethoxysilyl) cyclohexylsulfonyl azide,

2-methyl-4-(trichlorosilyl)butylsulfonyl azide,

3-chloro-6-(trimethoxysilyl)hexylsulfonyl azide,

6-(trimethoxysilyl)hexylsnlfonyl azide,

2-(trichlorosilyl)ethylsulfonyl azide,

3-(dimethylaminodimethylsilyl)propylsulfonyl azide,

2- (triethoxysilyl ethylsulfonyl azide,

3-(methyldimethoxysilyl)-propylsulfonyl azide,

3-(trimethoxysilyl)propylsulfonyl azide,

4- [diethoxy- 4-sulfonylazidobutyl) silyl] butylsulfonyl azide,

p-(trimethoxysilyl)benzenesulfonyl azide,

2- (trimethoxysilyl ethylbenzenesulfonyl azide,

N-3- triethoxysilyl) propyl-N'-3-azidosulfonylpropylurea,

N-3- (triethoxysilyl propyl-N-m-azidosulfonylphenylurea, etc.

The nitrogen containing silane compounds of this invention can beprepared by various methods. The diazosilanes, for example, can beprepared by reacting the corresponding hydrochloride salt of the primaryamine with nitrous acid (diazotization), which can be shown as follows:

where T, X, R and R are as defined above. The intermediate aminosilanecan be prepared, for example, by the addition of the desired silane toan unsaturated ester of glycine as follows XS:i-(CH2):O( JCH2NHz Where Tand X are as defined above. If desired the unsaturated ester of glycinecan first be diazotized then reacted with the desired silane as follows:

where T and X are as defined above. Still another method for thepreparation of the diazosilanes is the reaction of a hydroxydiazoacetate with a silaneisocyanate as follows:

where T, X and R are as defined above and x is greater than 1.

The azidosilane compounds, for example, can be prepared by reacting thecorresponding chloro-substituted compound wtih an alkali metal azide. Inthe preparation of an azidoformate the reaction can be shown as follows:

where T, X, and R are as defined above. The intermediate silanechloroformate can be prepared, for example, by the addition of thedesired silane to an unsaturated chloroformate as follows:

where T and X are as defined above, or an epoxysilane can be reactedwtih phosgene as follows:

where T and X are as defined above, or an alkylsilane can bechlorosulfonated as follows:

where T and X are as defined above. It should be noted that a mixedreaction product may be obtained from chlorosulfonation, sincesubstitution is random along the alkyl chain and there will usually besome chlorination of the alkyl chain. Another method for the preparationof the azidosilanes is by reacting a compound containing the azido groupwith a compound containing the silane. In the case of sulfonyl azides anorganoaminosilane can be reacted wtih a compound containing both asulfonyl azide group and an isocyanate group as follows:

where T and X are as defined above and x is greater than 1.

Many of the nitrogen containing silane compounds of this invention areliquids, that is liquid at 2-0-25 C. and at atmospheric pressure.However, some are solids. They are characterized in that the diazo orazido portion readily reacts with a wide variety of polymers to eifectlinkage of the polymer to the silane compound. They are furthercharacterized in that the silane portion of the molecule adheres tomaterials such as siliceous materials, metals, metal oxides and manypolymers.

The above described nitrogen containing silane compounds readilycondense to form dimers, trimers and even polymers when heated and/or inthe presence of water and acidic or basic condensation catalysts.Because of the case with which they condense, it is apparent that manyof the silane compounds of this invention (with the exception of thosefreshly prepared under anhydrous conditions) exist in admixture with atleast a small amount of their condensation products. Therefore, it is tobe understood that the terms nitrogen containing silane compound andsilane compound, used in the specification and claims of thisapplication, include not only the pure monomeric compounds but alsomixtures of the monomers with at least a small amount of thecondensation products of the monomers. It may be desirable in some casesto use a condensation product of a nitrogen containing silane compoundinstead of the monomer. If this is desired such condensation product canreadily be prepared by heating one of the above described silanecompounds in the presence of a small amount of water and a conventionalcondensation catalyst, i.e. acetic acid, HCl, HBr, 'NaOH, NH OH, or thelike. A typical dimer would have the general formula where T, R, Z, cand d are as defined above. A typical condensation polymer would havethe general formula The following examples will illustrate the inventionall parts and percentages being by weight unless otherwise indicated.

EXAM PLE 1 This example illustrates N-3-(triethoxysilyl)propyl-N'-m-azidosulfonylphenylurea, and a process for its preparation.

To a solution of 15 parts of m-azidosulfonylphenyl isocyanate in 150parts of benzene at room temperature was added dropwise 14.8 parts of3-aminopropyltriethoxysilane with stirring. As the triethoxysilane wasadded, a white needlelike solid began to form. The addition of 25 partsof methylene chloride resulted in a clear solution. After stirringovernight the solvent was evaporated leaving a yellow solid having amelting point of -95 C.

An infra-red spectrum of this product showed a strong azide band at 2130cm.- and a strong carbonyl band at 1700 cmf A sample of the productdecomposed in diphenyl ether at 153 C. evolving 92% of the theoreticalamount of gas.

A typical elemental analysis of this product was.--

Analyzed (percent): N, 14.6; S, 7.3; Si, 6.2. Calculated (percent): N,15.7; S, 7.2; Si, 6.4.

A sample of the product recrystallized from a mixed benzene-hexanesolvent was white and melted at 95- 97 C.

EXAMPLE 2 This example illustrates 3-(methyldimethoxysilyl)propylazidoformate and a process for its preparation.

To a solution of methyldichlorosilane parts) and allyl chloroformate (60parts) was added chloroplatinic acid (0.0052 part) dissolved inisopropanol (0.1 part). The mixture thus formed was stirred at 2025 C.under nitrogen for about 144 hours. Volatiles were removed by aspiratorvacuum from the reaction mixture. Subsequently the reaction mixture wasvacuum distilled. A middle cut (35 parts) boiling at 65-68 C. at apressure of 0.4 millimeter of mercury was collected as the desiredintermediate product. It consisted essentially of3-(methyldichlorosilyl) propyl chloroformate.

A portion (21 parts) of this intermediate product was added to a slurryof sodium azide (46.2 parts) in anhydrous methanol parts). The resultingmixture was stirred rapidly in a nitrogen atmosphere for about 144 hoursat 20-25 C. The reaction mixture was placed under aspirator vacuum toremove solvent. The residue, a pasty solid, was extracted with methylenechloride. The colorless extract solution was subjected to vacuum toremove substantially all of the solvent. The residue was a colorless oil(37.6 parts) consisting essentially of 3- (methyldimethoxysilyl)propylazidoformate.

A typical elemental analysis of this product was.- Analyzed (percent):N, 16.2; Si, 12.1; C1, 0.1. Calculated (percent): N, 18.0; Si, 12.0;Cl,0.

EXAMPLE 3 This example illustrates 3-(trimethoxysilyl)propylazidoformate and a process for its preparation.

To a solution of trichlorosilane (67.5 parts) and allyl chloroformate(30 parts) was added a solution of chloroplatinic acid (0.0052 part) inisopropanol (0.1 part). The resulting mixture was stirred for 45 hoursat 20-25 C. It was then subjected to vacuum distillation, the fractiondistilling at 48-50 C. at a pressure of 0.35 millimeter of mercury beingcollected as the desired intermediate product (28 parts). This productconsisted essentially of 3-(trichlorosily1) propyl chloroformate.

This intermediate product (23 parts) was added dropwise to a slurry ofsodium azide (39 parts) in anhydrous methanol 100 parts) whilemaintaining the reaction mixture thus formed at 20-25 C. After stirringat this temperature in a nitrogen atmosphere for 20 hours, the reactionmixture was sparged with nitrogen and then stripped by aspirator vacuumof solvent. The white pasty residue Was extracted with methylenechloride, the solids-liquid separation being achieved by centrifugationand decantation. The remaining solids were extracted two more times withfresh methylene chloride with the resulting methylene chloride extractsbeing combined with the first methylene chloride extract. The totalmethylene chloride extract was subjected to aspirator vacuum and thenhigh vacuum (0.5 millimeter of mercury) at 2025 C. The residue was acolorless liquid (19.9 parts) consisting essentially of3-(trimethoxysilyl)propyl azidoformate.

An infra-red spectrum of this product showed a strong azide doublet at2140 cm.- and 2180 curand a strong carbonyl band at 1740 cm.-

A typical elemental analysis of this product was. Analyzed (percent): N,16.6; Si, 10.1; Cl, 0.81. Calculated (percent): N, 16.8; Si, 11.2; C1,0.

EXAMPLE 4 This example illustrates 2-chloro-3-[3-(trimethoxysilyl)propoxyJpropyl azidoformate, and a process for its preparation.

Liquid phosgene (20 parts) was added to a flask containing pyridine (1part) at 60" C. The resulting yellow slurry was warmed to 15 C. and3-glycidoxypropyl trimethoxysilane (23.6 parts) added dropwise over a 30minute period. The yellow reaction mixture was stirred for 1.5 hours at15 to 10 C., and then placed in a wet ice bath (+3 C.) under a very slownitrogen sparge. The wet ice bath was allowed to warm to 2025 C.

over a period of 16 hours. The resulting reaction mixture- (a tancolored slurry) was sparged with nitrogen and then subjected to highvacuum at 2025 C. The residue was a light amber oil containing a smallquantity of white solids. The solids were separated from the oil bycentrifugation, to give the desired intermediate product (29 parts).This intermediate product consisted essentially of 2-chloro 3[3-(trimethoxysilyl)propoxy]propyl chloroformate.

A portion (13.4 parts) of the intermediate product was added dropwise toa slurry of sodium azide (7.8 parts) in anhydrous methanol (100 parts)maintained at 2025 C. The resulting reaction mixture was stirred for 20hours at 2025 C. under nitrogen. The white slurry thus obtained wasstripped under aspirator vacuum and then extracted with methylenechloride. The extract was subjected to high vacuum at 2025 C. to removesubstantially all of the solvent. The resulting product was an oil (12.5parts), consisting essentially of2-chloro-3-[3-(trimethoxysilyl)propoxy]propyl azidoformate.

The infra-red spectrum of this product showed a strong azide doublet at2140 cm.- and 2185 cm. as well as a carbonyl band at 1740 cm.-

A typical elemental analysis of the product was.-Analyzed (percent): N,11.6; Si, 7.7; Cl, 10.8. Calculated (percent): N, 12.3; Si, 8.2; Cl,10.4.

EXAMPLE This example illustrates 3(triazidosilyl)propyl azidoformate anda process for its preparation.

Liquid sulfur dioxide (40 parts) was collected in a dry ice-acetonebath, warmed to 20 C., and sodium azide (3.25 parts) admixed with it.While stirring the resulting white slurry at C., a portion (2.56 parts)3-(trichlorosilyl)propyl chloroformate was added. The reaction mixturethus formed was stirred at 10" C. for 3 hours and then allowed to slowlywarm to 25 C. while passing a stream of nitrogen through the reactionmixture and evaporating excess sulfur dioxide. Methylene chloride (60parts) was added to the remaining white solid material, and the mixturewas then centrifuged to remove insoluble material. The solution was thenstripped of methylene chloride by sparging with a stream of nitrogenuntil a constant weight was reached. The material that remained was acolorless oil (2.49 parts) consisting essentially of3-(triazidosilyl)propyl azidoformate.

The infra-red spectrum of the oily product displayed a strong azide bandat 2160 cm. as well as a carbonyl band for the azidoformate at 1730 cmrThe azide content of the oil analyzed 59.2%. The calculated azidecontent for 3-(triazidosilyl)propyl azidoformate is 59.5%.

EXAMPLE 6 This example illustrates mixed isomers of chlorinated(trimethoxysilyl)amylsulfonyl azide and a process for their preparation.

Amyltrichlorosilane (41 parts) in carbon tetrachloride (250 parts)containing pyridine (0.5 part), was exposed to ultraviolet light whilesulfuryl chloride (48.5 parts) was added dropwise over a period of 1hour. The temperature was maintained at 2530 C. during the addition. Themixture thus formed was stirred for 7 hours at 25-30 C. with continuedexposure to ultraviolet light. A slightly cloudy solution resulted.Volatiles were removed from the solution by heating to C. at atmosphericpressure, and then subjecting it to high vacuum at 20-25 C. The productthat remained was an amber oil (54 parts) consisting essentially ofmixed isomers of chlorinated (trimethoxysilyl) amylsulfonyl chloride.

A portion (45 parts) of the intermediate product was added dropwise to aslurry of sodium azide (57 parts) in anhydrous methanol (300 parts)maintained at 2025 C. The resulting reaction mixture was stirred at 2025C. for 20 hours, and then the methanol removed at this temperature byaspirator vacuum. The residue was a reddish tan pasty solid material. Itwas diluted with methylene chloride and the solids removed bycentrifugation. The yellow solution remaining was subjected, at 2025 C.,to a vacuum of 0.5 millimeter of mercury to remove the methylenechloride. The residue was a yellow oil (39.4 parts) consistingessentially of mixed isomers of chlorinated(trimethoxysilyl)amylsulfonylazide.

The infra-red spectrum of the product in methylene chloride shows anazide band at 2145 cm.- and sulfonyl bands at 1370 cm." and 1190 cm.-

A typical isomer contains one chloride on the amyl chain and onesulfonyl azide group also on the amyl chain.

EXAMPLE 7 This example illustrates mixed isomers of(trimethoxysilyl)hexylsulfonyl azide and a process for theirpreparation.

A solution of n-hexyltrichlorosilane (102 parts) in methylene chloride(1200 parts) was cooled to 3 C. Sulfur dioxide gas was bubbled throughthe solution at a rate of about 9 parts per hour for about 10 minutes.Chlorine gas (25 parts) was then introduced in conjunction with thesulfur dioxide gas over a 5 hour period into the reaction mixture at 5C. while exposing to ultraviolet light. The solvent was removed byaspirator vacuum from the chlorosulfonated reaction mixture. Theresulting pale yellow solution was subjected to Vacuum distillation upto 65 C. at an ambient pressure of 0.5 millimeter of mercury to removeunreacted n-hexyltrichlorosilane. The oily residue (345 parts) was anintermediate product consisting essentially of mixed isomers of(trimethoxysilyl)- hexylsulfonyl chloride.

A quantity (159 parts) of the intermediate product was added dropwise toa slurry of sodium azide parts) in anhydrous methanol (850 parts) whilemaintaining the temperature at 20 25 C. After stirring the reactionmixture at this temperature for about 20 hours, the pink slurry wassparged with nitrogen and then stripped by aspirator vacuum of solvent.Benzene (450 parts) was admixed with the reaction mixture and the thusdiluted mixture filtered. The filtrate was washed with fresh benzene(250 parts) and the wash liquid and filtrate combined to give a clearcolorless solution (800 parts). This solution was stripped of benzene at35 C. at an ambient pressure of 0.5 millimeter of mercury. The residuewas a colorless oil (142 parts) consisting essentially of mixed isomersof (trimethoxysilyl)hexylsulfonyl azide.

An infra-red spectrum of the product showed an azide band at 2130 cm.-as well as sulfonyl peaks at 1365 cm." and 1160 cmr- A typical elementalanalysis of the product was. Analyzed (percent): N, 12.8; S, 9.7; totalCl, 2.6. Calculated (percent): N, 13.5; S, 10.3; total Cl, 0.

The small amount of chlorine found in the analysis of the productindicates that the hexyl chain was partially chlorinated.

EXAMPLE 8 This example illustrates mixed isomers of(trimethoxysilyl)cyclohexylsulfonyl azide and a process for theirpreparation.

A solution of cyclohexyltrichlorosilane (100 parts) in methylenechloride (1200 parts) was cooled to 3 C. and sulfur dioxide .gas bubbledinto the solution at a rate of 11.8 g. per hour for a period of about 15minutes. While exposing the reaction mixture to ultra-violet light,chlorine gas (32.5 parts) was introduced into the reaction mixture inconjunction with the sulfur dioxide gas over a period of about 5 hours.Upon completion of the introduction of chlorine gas, exposure of thereaction mixture to ultraviolet light was continued for an additional 30minutes. The solvent was removed from the clear solution under aspiratorvacuum and then unreacted material was removed by distillation at 40 C.and pressure of 0.5 millimeter of mercury. The yellow oily residue (66parts) consisted essentially of mixed isomers of(trichlorosilyDcyclohexylsulfonyl chloride.

This intermediate product (60 parts) was added dropwise to a slurry ofsodium azide (74 parts) in anhydrous methanol ("500 parts). Theresulting mixture was stirred at 20-25 C. in a nitrogen atmosphere for20 hours. After removal of methanol by aspirator vacuum, benzene (300parts) was admixed with the reaction mixture and the resulting slurrycentrifuged to remove insolubles. The liquid that remained was a clearpale yellow solution. By subjecting the solution to a vacuum of 0.5millimeter of mercury at a temperature of about 30 C., the benzene wasstripped from the solution, giving a yellow oily product (45.5 parts)consisting essentially of mixed isomers of(trimethoxysilyl)cyclohexylsulfonylazide.

An infra-red spectrum of the product showed a strong azide peak at 2145cm.- and sulfonyl bands at 1370 cm.- and 1160 cmr A typical elementalanalysis of the product was. Analyzed (percent): N, 11.6; S, 8.6; Si,8.9; total Cl, 3.1. Calculated (percent): N, 13.6; S, 10.3; Si, 9.05;total Cl,

The small amount of chlorine found in the analysis of the productindicates that the cyclohexyl ring was partially chlorinated.

EXAMPLE 9 This example illustrates 3(trimethoxysilyl)propyl diazoacetateand a process for its preparation.

A mixture of glycinyl chloride hydrochloride (13 parts) and allylalcohol (11.6 parts) was heated under an atmosphere of nitrogen for 2hours at 90 C. The resulting mixture was extracted thoroughly with etherto remove excess allyl alcohol and the remaining insoluble materialdissolved in water (50 parts). Ether (180 parts) was added to theaqueous solution and sodium nitrite (6.9 parts) dissolved in the aqueouslayer while maintaining the temperature at 0 C. Then 10% sulfuric acidwas added dropwise until the ether layer became bright yellow. The etherlayer was separated from the aqueous layer and dried over a mixture ofanhydrous sodium sulfate and anhydrous sodium carbonate. The dryingagents were filtered off and the ether removed under vacuum. The yellowoily residue consisted essentially of allyl diazoacetate.

A portion of the intermediate product parts), along wth trimethoxysilane(12.2 parts) and a catalytic amount of azo bis-isobutyronitrile weredissolved in benzene (175 12 parts) and heated for 16 hours at 50 C. Thebenzene and excess silane were then removed under vacuum. The yellowoily residue consisted of 3(trimethoxysilyl)propyl diazoacetate insubstantial yield.

EXAMPLE 10 This example illustrates mixed isomers of 3- and4-(trimethoxysilyDcyclohexyl diazoacetate and a process for theirpreparation.

A mixture of glycinyl chloride hydrochloride (9 parts) and3-cyclohexene-l-ol (14.7 parts) was heated under an atmosphere ofnitrogen for 2 hours at C. The resulting mixture was extractedthoroughly with ether and the remaining insoluble material dissolved inwater (40 parts). Ether parts) was added to the aqueous solution andsodium nitrite (4.7-6 parts) dissolved in the aqueous layer whilecooling the whole to a temperature of 0 C. Then 10% sulfuric acid wasadded dropwise until the ether layer became bright yellow. The etherlayer was separated and dried as described in Example 9. The dryingagents were filtered off and the ether removed under vacuum. Theremaining yellow oil consisted essentially of3-cyclohexene-l-diazoacetate.

A portion of the intermediate product (4.2 parts), along withtrimethoxysilane (12.2 parts) and a catalytic amount of azobis-isobutyronitrile were dissolved in benzene parts) and heated for 14hours at 50 C. The benzene and excess silane were then removed undervacuum. The yellow oily residue consisted essentially of 3 and4-(trimethoxysilyDcyclohexyl diazoacetate in substantial yield.

EXAMPLE 11 This example illustrates p-[3-(trimethoxysilyl)propyl] phenyldiazoacetate and a process for its preparation.

Glycinyl chloride hydrochloride was reacted with3-(phydroxyphenyD-l-propene and then diazotized using the processdescribed in Examples 9 and 10.

The resulting intermediate (9.1 parts), along with trimethoxysilane(12.2 parts) and a catalytic amount of azo bis-isobutyronitrile weredissolved in benzene 130 parts) and heated for 15 hours at 50 C. Thebenzene and excess silane were removed under vacuum. The yellow oilyresidue'consisted essentially of p-[3-(trimethoxysilyl)propyl]phenyldiazoacetate in good yield.

EXAMPLE 12 This example illustrates 10-[(3-trimethoxysilylpropyl)carbamoyl] decyl diazoacetate and a process for its preparation.

To melted 1,10-decanediol (35 parts) at 125 C. was added glycinylchloride hydrochloride (11.24 parts) portionwise under an atmosphere ofnitrogen over a one hour period with stirring. The resulting mixture washeated under nitrogen for 2 hours at 120 C. Water (500 parts) was addedand the mixture stirred 4 hours. It was then extracted four times withportions of chloroform (300 parts). The aqueous layer was filtered andevaporated to dryness to give an orange gummy solid. The solid wasextracted with ether and dissolved in water (100 parts). Ether (210parts) was added to the resulting yellow aqueous solution andthe-mixture cooled to 0 C. Sodium nitrite (50 parts) was dissolved inthe aqueous layer and 10% sulfuric acid added dropwise. With theaddition of acid the ether layer became yellow and was periodicallydrawn OE and replaced with fresh ether. The combined ethereal extracts(850 parts) were dried as described in Example 9. The drying agents werefiltered off and the ether removed under vacuum. The remaining yellowoil (6.4 parts) consisted essentially of 10-hydroxydecyl diazoacetate.

A portion of the intermediate product (5.63 parts), along with3-(trimethoxysilynpropyl isocyanate (4.76 parts) and a few drops ofdibutyl tin dichloride were added to benzene (45 parts) and stirred for5 days under an atmosphere of nitrogen at room temperature. The

13 benzene was then removed under vacuum leaving a yellow oily product.The resulting product was -[(3-trimethoxysilylpropyl)carbamoyl]decyldiazoacetate of approximately 81% purity as determined by nitrogenevolution.

EXAMPLE 13 mediately dried with a cold air gun. Samples of each polymerwere cut into 0.050 inch thick 1 x /2 inch plaques, cleaned and placedbetween two metal panels so that the panels overlapped approximately /2inch. Each assembly was molded in a hydraulic press for 5 minutes at anelevated temperature and a pressure of 400 p.s.i. and then cooled in thepress to room temperature. In each case the assembly was placed in a jigduring the molding to maintain a 0.025 inch glue line. Each sample wasthen tested for lap shear strength. The metal panels and polymers used,the temperature of the pressure molding and the results of the lap shearstrength tests are tabulated below.

2 High dcnstg' polyethylene having a specific gravity of 0.952 g.lcc.and amelt index (I;

at 190 C I High density polyethylene having a specfiic gravity oi 0.945g./cc.

mixed aliphatic hydrocarbon solvent, having a boiling point of 165 C. to200 C., was divided into four portions. To each portion of the colloidalsuspension was added a different amount of2-chloro-3-[3-(trimethoxysilyl)propoxy]propyl azidoformate in amethylene chloride solution. Each suspension was mechanically mixed andthen used to dip-coat an iron phosphate treated steel panel. Each coatedpanel was baked at a temperature of 400 F. for eight minutes and thenallowed to cool. The coating on each panel was tested for adherence byscoring with a razor blade and then drawing the edge of a metal coinfirmly across the thus scored surface. The adhesion of the coating tothe surface was rated as follows:

Poor-the coating strips easily from the substrate Faira major part ofthe coating is removed but very noticeable resistance to the coin isnoted Good-a minor part of the coating is removed. The coin skips acrossthe coating rather than removing a continuous film Excellent-None of thecoating is removed.

The results of the test are tabulated below:

Percent of azidosrlane Adhesion Poor.

Good. Excellent.

suspension 1 Percent by weight based on the weight of polypropylene.

1 Control.

EXAMPLE 14 EXAMPLE 15 This example shows the bonding of polypropylene tometal panels by first treating the panels with an azidosilane compound.

Metal panels 1 x 4 inches and inch thick were cleaned and then treatedwith a methylene chloride solution of an azidosilane compound exactly asdescribed in Example 14. The panels were assembled for lap shearstrength tests by placing plaques of polypropylene between two panelsalso as described in Example 14 and molding at a temperature of 230 C.for 5 minutes. The time was used as follows: 3 minutes at contactpressure, 1 minute up to a pressure of 200 p.s.i. and 1 minute atpressure. Each molded sample was then tested for lap shear strength. Themetal panels used, the azidosilane compound used and its concentrationin the methylene chloride solution and the results of the tests aretabulated below.

Lap shear (ionccenborld ra lon, stren t Azidosilane gJml. Metal panel p.s.1

Sulfonyl azide 0. 005 Cold rolled steel- D 0.01 ......do 810 Do 2,400 D02, 600 Do 250 Do-. 600 1 )o 0.04 .--.-do 1,600 3-(trlmethoxysilybpropyl0. 005 Cold rolled steel- 240 a oformate.

0.04 do 1,400 0.01 Aluminum. 980 .04 do 1,900 0. 02 Cold rolled steel.2, 000

1 Mixed isomers of (trimethoxysilyl)hexylsulionyl azide described inExample 7.

M ixed isomers of chlorinated (trimethoxysilyl)amylsulfonyl azidedescribed in Example 6.

EXAMPLE 16 This example shows the bonding of a polypropylene suspensionto metal panels by first treating the panels with an azidosilanecompound.

The procedure used in this example is similar to that described inExample 14 except the panels were treated by dipping in a 5% aqueousmethanol solution of 0.02 g./ ml. of 3 (trimethoxysilyl)propylazidoformate. Each panel was coated on one side, using a 10 mil drawdownknife, with the colloidal suspension of crystalline polypropyleneparticles described in Example 13. The coatings were fused at 190-200 C.for 7 minutes. The resulting films'were approximately 0.7-1.0 mil inthickness. Plaques (40 mils thick) of the crystalline polypropylene filmdescribed in footnote 1 of Example 14 were placed between the coatedpanels as described in Example 14 and molded as described in Example 15.The molded samples were then tested for lap shear strength and theresults tabulated below:

Lap shear bond strength EXAMPLE 17 This example shows the bonding of apolypropylene suspension to metal panels and lap shear bond strengthtests where the polypropylene is first mixed with an azidosilanecompound.

Samples of the colloidal suspension of crystalline polypropyleneparticles described in Example 13 were mixed with various amounts ofazidosilane in methylene chloride solution.

Metal panels were coated with the polymer suspension and fused asdescribed in Example 16. Then the coated panels were assembled andmolded also as decribed in Example 16. The molded samples were testedfor lap shear strength. The metal panels used, the azidosilane compoundused and the amount and the results of the tests are tabulated below:

1 Percentage by weight based on the weight of polypropylene. 1 Asdescnbed in footnote 1 of Example 16.

EXAMPLE 18 This example shows the bonding of polypropylene to glasscloth which has first been treated with an azidosilane compound.

Twelve (12) ply laminates of glass cloth and polyproplyene film wereprepared using 181 style electrical glass woven cloth, heat cleaned andhaving a weight of 8.9 ounces per square yard and 5 mil film ofcrystalline polypropylene. Sheets of the glass cloth were first immersedin a 0.09 g./ml. solution of 2-chloro-3[3-(trimethoxysilyl)propoxy]propyl azidoformate in methylene chloride. The thus treatedcloth was dried and then laid up to form the laminate by alternatingplies of the treated glass cloth and sheets of the polypropylene film.The resulting assembly was compression molded at a temperature of 220 C.for 7 minutes at contact pressure, 3 minutes at a pressure of 440 p.s.i.and then cooled to 23 C. under 440 p.s.i. pressure to form a inch thicklaminate. A control laminate was prepared exactly as described aboveexcept the treatment with the azidosilane was omitted. Test specimens 1inch by 3 inches were cut from the laminates and tested for fiexuralstrength and flexural modulus ac- 16 cording to ASTM D-790 on a 2 inchspan at 0.05 inch/ minute crosshead speed. The results are tabulatedbelow:

EXAMPLES 19-30 These examples show the bonding of various polymers toglass cloth which have first been treated with an azidosilane compound.

Strips of the glass cloth described in Example 18 were immersed in a0.5% by weight solution of 2-chloro-3[3- (trimethoxysilyl)propoxy]propylazidoformate in methylene chloride, drained, and hung to dry. Theresulting treated glass cloth was used to prepare 12 ply laminates with12 difierent polymers as follows:

(19) Strips of the treated glass cloth were immersed in a 12.5% byweight solution of polycarbonate resin in methylene chloride. The stripswere hung up to dry and then heated in an oven at a temperature of 70 C.to remove the last traces of solvent. The resulting sheets were cut intosquares measuring 5% x 5% inches. Twelve plies of the polymerimpregnated cloth were assembled for molding.

(20) A twelve ply assembly was prepared exactly as described in 19except the strips were immersed in a 33% by weight solution ofacrylonitrile-butadiene styrene molding powder in methylene chloride.

(21) A strip of the treated glass cloth was cut into squares measuring 5/8 x 5% inches. A laminate was assembled by alternating 12 plies of theglass cloth squares with 13 plies of crystalline polypropylene film 5mils in thickness.

(22) A laminate was assembled exactly as described in 21 except thepolymer was 6 mil polyethylene.

(23) A laminate was assembled exactly as described in 21 except thepolymer was 5 mil pressed sheets of polystyrene.

(24) A laminate was assembled exactly as described in 21 except thepolymer was 5 mil pressed sheets of polyoxymethylene.

(25) A laminate was assembled exactly as described in 21 except thepolymer was 5 mil poly(vinyl chloride) film.

(26) A laminate was assembled exactly as described in 21 except thepolymer was 5 mil nylon film.

(27) A laminate was assembled exactly as described in 21 except thepolymer was 6 mil poly(ethylene terephthalate) film.

(28) A laminate was assembled exactly as described in 21 except thepolymer was 6 mil poly(ethylene terephthalatehexahydroterephthalate)film.

(29) A laminate was assembled using 12 squares of the treated glasscloth. Each square measured 5% x 5% inches and was coated with a hotepoxy resin. The resin was prepared by heating 15 parts of the epoxyresin to 50 C. and adding 1.87 parts of m-phenylenediamine. The laminatewas assembled on a heated 12 x 12 inch steel plate fitted with apoly(ethylene terephthalate) release sheet. An excess of resin wasmaintained on the laminate at all times and as each square of cloth wasadded, a spatula was used to work the trapped air through the cloth. Oneeighth inch spacer bars were placed on three sides of the laminate and arelease sheet placed on top. A second steel plate was placed on thelaminate and the entire assembly secured with C-clamps.

(30) A laminate was assembled exactly as described in 29 except thepolymer was a styrene-modified polyester resin mixed with 1 part perhundred methyl ethyl ketone peroxide and heated to 60 C.

All thermoplastic laminates were prepared by compression molding in apicture-frame mold having inside di- 17 mensions of 6 x 6 x Ms inches.Molding conditions are given in Table I.

The thermosetting plastic laminates were gelled and cured while clampedbetween steel plates. The conditions 18 EXAMPLES 31 AND 32 Theseexamples show the bonding of polypropylene to samples of glass clothwhich have first been treated with an azidosilane compound.

are given in Table II.

TABLE I Preheat Molding Cooling, Time, Temp, Press., Time, Temp, Presspress., Polymer min. C. p.s.i. min. C. p.s p.s.i.

Example Number:

19 Polycarbonate 4 250 Contact.-- 5 250 500 500Acrylonitrile-butadiene-styrene 7 240 do.. 5 240 350 350 Polypropylene 7220 -do.. 5 220 400 400 Polyethylene 6 177 -do..- 4 177 400 400Polystyrene 6 204 .do 4 204 340 340 Polyoxymethylen 4 220 do. 3 220 340340 Poly(vlnyl chloride) 193 ..do.- 3 193 440 440 Nylon 8 10 280 do 2280 500 500 Poly(ethylene terephthalate) L-.- 7 285 .do 5 285 500 11 50028 Poly(ethylene terephthalate 4 235 do 3 235 400 11 400hexahydroterephthalate) 1 Based on 4,4-dihydroxydipheuylpropane andhaving a melt index (ASTM D-1238) of 5 g./10 min. i 19% acrylonitrlle,butadiene having a melt index (ASTM D-1238) of 16 g./l0 min.

8 Crystalline, having a specific gravity of 0.904 g./cc. and a meltindex of 4 g./10 min. (12 at 230 0.).

4 High density, having a specific gravity of 0.952 g./cc. and a meltindex of 0.6 g./l0 min. (Ia at 190 0.).

l Atactic polystyrene having a specific gravity of 1.04 g.lcc. 5 Havinga specific gravity of 1.42 g./cc. 7 Rigid, having a number averagemolecular weight of 140,000.

I Poly(hexamethylene adipamide) having a number average molecular weightof 110,000. 9 Having an intrinsic viscosity of 0.61 and an amorphousspecific gravity oi 1.34 g./cc. 10 Having a specific viscosity of 0.85at C. in a 60/40 solution of phenol and tetrachloroethane and a specificgravity of 1.335

g./cc. after annealing.

ll Annealed for 2 hours at 135 C. under pressure.

1 Epoxide resin-diglyeidyl ether of bisphenol A having an expoxideequivalent weight of 190.

9 Styrene-modified bisphenol-type polyester.

Control samples were prepared exactly as described above except theglass cloth was not first treated with the azidosilane compound. Samplesof the treated and control laminates were tested for flexural strengthand modulus according to ASTM D-790 using a 2 inch span, singlepointloading, and a crosshead speed of 0.2 inch/minute. Each sample was cutto a size of 1 x 3 x /s inch. Tests were also conducted on most of thesamples after boiling in water. The results of the tests are set forthin Table III.

Strips of the glass cloth described in Example 18 were immersed insolution of an azidosilane in methylene chloride, drained and hung todry. The resulting treated glass cloth was used to prepare 12 plylaminates with crystalline polypropylene film, 5 mils in thicknessexactly as described in Example 18. Control samples were prepared in thesame manner except the glass cloth was not first treated with anazidosilane compound. Samples were cut from the treated and controllaminates and tested for flexural strength and modulus according to ASTMD- 790. Tests were also conducted on the samples after boil- TABLE IIIDry fiexural properties Boiled in water properties Treatment ofStrength, Modulus, Hours Strength, Modulus, Polymer glass cloth p.s.i.p.s.i.X10 boiled p.s.i. p.s.i. 10 Exargple num er:

7 Treated. 52,200 2.7 72 24 000 2.2 19 "{Control- 39, 200 2.4 72 2113002.0 20 Ac y o i fl w --{5332f}; $288 318 Z; 2% 2 Treated. 38, 2. 2 7231, 000 2. 1 21..--.-. Polypropylene l 1 g 2( g reate ea 6 "iggntro.-. 2g 72 18,200 2.0 eate 24 Po yo ym r 24:500 22 I Treated..- 32,100 2.6 7215,500 1.8 25 P 1YMBY1 chhride) "{Control--. 22,800 2.0 72 ,10 26 N l nTreated--. 56,600 2.8 72 30,500 1.8 y Control... 43, 000 3.6 137,(200 1. 4 27 4 Poly(ethylene terephthalate).--.. 83323 12 I 28Poly(ethylene terephthalate {Treatedrn 46,700 2.6 12 26, 500 3.0hexahydroterephthalate). glonatg d..- 46, 12,306?) g) ea e Control51,300 2.0 72 251000 2 e ing in water. The results of the tests are setforth in were cut from the treated and control laminates and testedTable IV. for fiexural strength and modulus according to ASTM TABLE IVDry fiexural 72 hour boil Azidosilane properties flexural propertiescone. (wt.

percent) Strength, Modulus, Strength, Modulus, Example No. .Azldosllanein CHzClz p.s.i. p.s.l. 10 fl p.s.i. p.s.i.X10 8 Control 12, 500 1. 8 8,100 1. 4 Sulfonyl azide 125 36, 100 2.5 21,100 1.8 31 .do 0 250 39,4002.4 24,300 2.2 do 0 500 45,100 2.3 24,000 2.4 do 1. 00 36, 400 2. 0 20,300 2. 4 -(trirnethoxys yl)-propyl 0.125 35,900 2.5 28, 400 2.1 32azidotormate.

------------------- do 0.250 35,200 2.5 25,600 2.2 -do 0. 500 32, 300 2.0 21, 500 2. a

1 As described in footnote 2 of Example 15.

EmiMPLE 33 D-790. Tests were also conducted on the samples after Alaminate was prepared exactly as described in Examboiling in water for72 hours. The results of the tests are pie 32 except the glass cloth wasimmersed in an aqueous set forth in Table V.

TABLE V Dry flexural 72 hour boil flexural Azidosilane propertiesproperties conc. (wt. percent) in Strength, Modulus, Strength, Modulus,Example No. Azidosilane solvent Solvent p.s.i. p.s.i.X p.s.i p.s.i.X10

C trol N 13, 300 1. 7 9, 800 1 4 0 34 Sulfonylazldek" 35,700 2.3 27,4002.1 31, 200 2.1 24, 100 2.1 it t? 3288 5'3 .900 sulmnylazmem 40,000 2.5,000 2.5 42, 000 2. 4 24, 500 2. 5

1 Mixed isomers of (trimethoxysilyl) cyclohexylsullonyl azide.

I As described in footnote 1 of Example 15. solution of the azidosilaneinstead of a methylene chloride EXAMPLE 36 solution. The aqueoussolution was prepared as follows. 35 A methylene chloride solutioncontaining 0.0024 g./ml. of 3-(trimethoxysilyl)propyl azidoformate wasdiluted with equal parts of acetone. The resulting solution was heatedto distill off the methylene chloride. A portion of the resultingacetone solution amounting to 33 ml. was diluted to a total volume of200 ml. with distilled water. Then the pH of the solution was adjustedto 4 with glacial acetic acid.

A sample of the laminate and a control were tested for flexural strengthand modulus as described in Examples 31 This example shows the bondingof a mixture of polypropylene and poly(vinyl acetate) to samples ofglass cloth by treating the said cloth with an aqueous sizing systemcontaining an azidosilane and a dispersion of the polymers.

Strips of the glass cloth described in Example 6 were immersed in anaqueous dispersion prepared as follows. To 200 parts of water containinga small amount of alkylphenoxy poly(ethyleneoxy ethanol) nonionicsurfactant was added with vigorous agitation 10 parts (based on thesolids) of an aqueous dispersion of poly(vinyl acetate) and 32. Theresults of the tests are tabulated below. having a B kfi ld viscosity f10 poises at 5 Q and a pH of 5.0. Then 10 parts of crystallinepolypropylene arfig g' 72 gf g g gicles, hsaving an average particlesize within the rang? of .02-0. micron, and 1 part of the mixed isomersof (triggg g'fgg g gg ifgg: gtgfigg methoxysilyl)hexylsulfonyl azidedescribed in Example 7 12 500 1 8 8 100 1 4 were added with continuedagitation. After immersion, the

211900 181200 strips were hung up to dry and then cut into 5% inchsquares for lamination. Twelve squares of the sized sheet EXAMPLES 34AND 35 were alternately laid up with 5 mil sheets of crystallinepolypropylene and compression molded at a temperature These examplesShow the bofldlng of P p py to of 220 C. for 7 minutes at contactpressure, 3 minutes sampl s f 81888 010th which have fi ee treated W ata pressure of 440 p.s.i. and then cooled to 23 C. under an azidosilanecompound. 440 p.s.i. pressure Test specimens were cut from the rip 0fthe glass cloth described in EXamPle 18 were laminates and tested forflexural strength and modulus acimmersed in benzene or methylenechloride solutions of cording to ASTM D-790 Tests were also conducted onan azidosilane, drained and hung to dry. The resulting the samples afterboiling in water for 72 hours. The retreated glass cloth was used toprepare 12 ply laminates results of the tests are tabulated below.

with crystalline polypropylene film, 5 mils in thickness ex- EXAMPLES3749 actly as described in Example 18. Control samples were Theseexamples show the bonding of variouspolymers prepared in the same mannerexcept the glass cloth was to glass cloth by first treating the polymerswith an not first treated with an azidosilane compound. Samples 75azidosilane.

22 In each example, 15 parts by weight of polymer was Strips of theglass cloth described in Example 18 were added to approximately 1300parts by weight of dry tetraimmersed in a 0.125% by weight solution ofmixed isochloroethylene. A methylene chloride solution of 0.67 part mersof 2-(trimethoxysilyl)ethylbenzenesulfonyl azide in by weight of3-(trimethoxysilyl)propyl azidoformate was benzene, drained, and hung todry. The resulting treated then added and the whole heated to 120 C.with stirring. 5 glass cloth was used to prepare 12 ply laminates withAfter 90 minutes the solution was cooled to 90 C. and l crystallinepolypropylene film 5 mils in thickness exactly part by weight of wateradded to promote silane hydroas described in Example 18. Control sampleswere prelysis. Strips of the glass cloth described in Example 18 paredin the same manner except the glass cloth was not were immersed forminutes in the hot solution, hung in first treated with an azidosilanecompound. Samples were a hood for 15 minutes and then dried for 16 hoursat 80 10 cut from the treated and control laminates and tested for C. ina vacuum oven. The dried strips were cut into 5% fiexural strength andmodulus according to ASTM D-790 inch squares. The thus coated clothsquares were laid up as described in Examples 31 and 32. The results ofthe to form the laminates by alternating plies of the cloth and testsare tabulated below:

5 mil sheets of the polymer. In each case the laminate contained 12plies of glass cloth. All laminates were prepared 15 Dry flexural 72hour be by compression molding in a picture-frame mold having propertiesflexuralpropertles inside dimensions of 6 x 6 x 41 inches. The moldingcon- Strength, Modulus, Strength, Modulus, ditions used for each polymerwere as descrlbed m Table p.s.i. p.s.i. x 10 p.s.i. p.s.i. X 10 Control12, 500 1. s s, 100 1. 4

Control samples were prepared exactly as described 20 Treated 37, 2002.4 32,100 2.1 above except the polymers were not first treated with theazidosilane. Samples of the treated and control laminates EXAMPLE 42were tested for fiexural strength and modulus according to ASTM D-790.The same tests were also conducted on This example shows the bonding ofpolypropylene to samples after bo111ng 1n water. The results of thesetests samples of glass cloth which have first been treated with are setforth in Table VI. an aqueous solution of an azidosilane compound.

TABLE VI Properties after Dry flexural properties boiling in waterTreatment of Strength, Modulus, Hours Strength, Modulus, Example No.Polymer polymer p.s.i. p.s.i. 10 boiled p.s.l. p.s.l.X10

87 yp py {Treated 1 g 3: 3 16,900 2 1 72 15,100 1.6 Polyethylene 013,200 1 2 72 8,200 1.3 39 Poly(ethylene terephthalate hexa- 49,400 3 124 15, 0 2.3 hydrotereph'thalate). Control 46,400 2 8 24 12,000 2.0

1 Crystalline, having a specific gravity of 0.904 g./cc. and a meltindex of 4 g./10 min. (I; at 230 0.).

9 High density, having a specific gravity of 0.952 g./cc. and a meltindex of 0.6 g./l0 min. (I at 190 0.).

I Prepared using mole percent dimethylhexahydroterephthalate and havinga specific viscosity 0.85 at 25 C. in a 60/40 solutlon of phenol andtetrachloroethane.

EXAMPLE 40 Strips of the glass cloth described in Example 18 wereimmersed in a 0.25% by weight aqueous solution of 3- This example showsthe bonding of polypropylene to (trimethoxysilyl)propylsulfonyl azide,drained, and hung samples of glass cloth which have first been treatedwith a to dry. The aqueous solution had been prepared by addingdiazoacetate silane compound. the sulfonylazide to water at a pH of 7.The resulting Strips of the glass cloth described in Example 18 weretreated glass cloth 2 usfid to P p laminates and i d i variousgoncentrafions f o- 3 tested exactly as descrlbed in Example 41. Theresults of silylpropyl)-carbamoyl] decyl diazoacetate in methylene thetests are tabulated below: chloride solution, drained, and hung to dry.The resulting fl a1 72h fl treated glass cloth was used to prepare 12ply laminates i g ggg g fg gg with crystallme polypropylene film, 5mlls. in thickness strength Modulus, Strength Modulus exactly asdescrlbed 1n Example 18. A control sample was p.s.l. p.s.1. x 10' p.s.l..s.1. X 10 prepared in the same manner except the glass cloth wasControl 12500 LS 81100 M not first treated with the diazoacetate silanecompound. Treated 38,150 2.2 21,000 1.8 Samples were cut from thetreated and control laminates and tested for flexural strength andmodulus according to EXAMPLE 43 ASTM D-790. Tests were also conducted onthe samples Thi example shows the bonding f polypropylene to afterboiling in water. The results of the tests are set forth samples ofglass cloth which have first been treated with in Table VII. anazidosilane compound.

TABLE VII Diazoacetate 72 hour boil silane flexural compound Dryfiexurel properties properties cone. (wt. Percent percent) in Strength,Modulus, Strength, Modulus, strength CH OI p.s.l. p.s.i. 10 p.s.l.p.s.i. 10 retention 0. 500 25, 200 1. 9 23, 400 1.9 92.7 0. 250 33, 5002. 1 23, 900 2.1 71. a 0. 125 as, 300 2. 1 2'7, 500 2. 2 82.1 None12,500 1 8 8,100 1.4 64.7

EXAMPLE 41 Strips of the glass cloth described in Example 18 were Thisexample shows the bonding of polypropylene to immersed in a 0.06% byweight solution of N-3-.(trisamples of glass cloth which have first beentreated with an ethoxysilyl) propyl-N-3-azidosulfonylphenylurea inbenazidosilane compound. 75 zene, drained, and hung to dry. Theresulting treated glass cloth was used to prepare laminates and testedexactly as described in Example 41. The results of the tests aretabulated below:

This example shows the bonding of polypropylene to samples of asbestosfelt which have first been treated with a diazosilane compound.

Laminates of asbestos felt and polypropylene film were prepared usingchrysotile asbestos felts, 10 mils in thickness (99% asbestos) and 10mil film of the crystalline polypropylene described in Example 18. Thefelts were first immersed in a 0.77% by weight solution of3-(trimethoxysilyl)propyl a-diazo oz carboethoxy acetate in methylenechloride. The thus treated felts were dried and then laid up to form thelaminate by alternating plies of the treated asbestos felt and sheets ofthe polypropylene film. The resulting assembly was compression molded ata temperature of 220 C. for 7 minutes at contact pressure, 3 minutes ata pressure of 440 p.s.i. and then cooled to 23 C. under 440 p.s.i.pressure to form a A; inch thick laminate. A control laminate wasprepared exactly as described above except the treatment with thediazosilane was omitted. Samples were cut from the treated and controllaminates and tested for flexural strength and modulus according to ASTMD-7'90. The results of the tests are tabulated below:

Flexural Flexural strength, modulus,

p.s.i. )(10 (p.s.i.)

Control- 15, 900 0. 9

Treated 18, 900 1.

EXAMPLE 45 This example shows the bonding of polypropylene to samples ofasbestos felt which have first been treated with an azidosilanecompound.

Strips of the asbestos felt described in Example 44 were immersed in a0.4% by weight solution of 3-(trimethoxysilyl)propylsulfonyl azide inmethylene chloride and dried. The resulting treated felt was used toprepare laminates with crystalline polypropylene and tested exactly asdescribed in Example 44. The results of the tests are tabulated below:

Flexural Flexural strength, modulus,

p.s.i. X10 (p.s.i.)

Control 15, 900 0. 9 Treated 19, 500 1. 1

EXAMPLE 46 TABLE VIII Diazo- Dry flexural 72 hour boil silane propertiesfiexural properties cone. (wt.

percent) Modulus, Modulus, in CH CI Strength, p.s.i. Strength, p.s.Sample p.s.i. X10" p.s.i. X10

Control- N one 13, 300 1. 7 8, 900 1. 2 a- 0.062 24,000 1. 8 12, 200 1.7 b 0. 26,900 1. 9 15, 200 1. 7 c- 0. 25 25, 200 1. 8 16, 700 1. 7 d 0.50 30, 200 2. l 17, 500 1. 9

EXAMPLE 47 This example shows the bonding of polypropylene to samples ofglass cloth which have first been treated with a diazosilane compound.

The procedure used in this example is the same as that described inExample 46 except the glass cloth was immersed in a 0.25% by weightdispersion of the diazosilane compound in water at a pH of 4-5. Theresulting laminates were treated as described in Example 18. The resultsof the tests are tabulated below:

This example shows the bonding of polyester tire cord to rubber tirestock using an azidosilane compound.

Poly(ethylene terephthalate) tire cord 1,000 denier and 3 ply, underabout 500 grams of tension was passed twice through a trough containinga 5% solution of 3-(trimethoxysilyl)propyl azidoformate in a mixedtrichloroethylene-methylene chloride solvent. The cord was next passedthrough two ovens in series at 200 F. and 400 F. Residence times in theovens were 65 and 54 seconds respectively. The cord dip pick-up wasapproximately 1.4% by weight.

The modified cord was next dipped in a resin latex prepared as follows.To a solution of 0.24 part of sodium hydroxide in 192.8 parts of waterwas added 8.8 parts of resorcinol with continued stirring until acomplete solution was achieved. Then 12.2 parts of 37% formaldehyde wasadded. The solution was aged for approximately 5 hours at about 75 C.and then added slowly to a mixture of 48 parts water and parts of acommercial latex, comprising a 41% solids terpolymer of styrene,butadiene and vinylpyridine. The monomers being present in a ratio ofapproximately 15:70:15. The mixture was stirred slowly for 15 minutesand its pH adjusted to 10.3 using concentrated ammonium hydroxide. Theresulting gray-violet latex contained approximately 20% solids. Theazidosilane treated cord was passed twice through a trough of the abovedescribed tire cord coating under a tension of 500 grams and then driedand cured for 54 seconds at a temperature of 480 F.

The thus coated cord was then embedded in a vulcanizable rubber tirestock and cured in the form of inch H- specimen. The rubber tire stockhad the following formulation:

25 The test specimens were cured for 45 minutes at a temperature of 307F. After several hours conditioning at room temperature the H-specimenswere tested according to the procedure of ASTM D-2138-62T. An average 26from the fabric. A control sample not treated with the azidosilaneseparated from the rubber at about 6 lbs./ in.

EXAMPLE 52 (6 test specimens) of 29 pounds was required to overcome Thisexample shows the use of an azidosilane compound the tire-cord rubberadhesion. A control-specimen treated to imp the Physical1 Properties ofglass bead fined exactly the same as above except for the azidosilanetreatpolypropylene. ment gave an average of 17 pounds required to over-Glass beads ranging in size from about 6 to 44 microns come the tirecord-rubber adhesion. A specimen treated and having a specific gravityof 2.48 grams/cc. were with the azidosilane as described above but nottreated 10 dipped to a et a ol Solution of y y with theresorcinol-formaldehyde latex dip gave an averethylbenzenesulfonylazide. The beads were dried, leaving age value between that reported forthe test specimens about 0.2% by weight pick-up of azidosilane compound.and that reported for the control specimens. The thus treated beads weredry blenderll in a mill with crystalline polypropylene having a me tindex (I at EXAMPLE 49 230 c. of 14 g., in a ratio of 30 parts of beadsto 70 Glass tire cord was bonded to rubber tire stock exactly parts ofpolymer by weight. The mixture was then screw as described in Example 48with the exception of heating injection-molded to form test specimens /2by A; by 5 the cord after it had been passed twice through the troughinches in size. Zone 1 of the injection molding machine containing thesolution of 3-(trimethoxysilyl)propyl aZidowas maintained at 440 F.,Zone 2 at 460 F., the nozzle formate. The test specimens were tested asdescribed in at 470 F., and the mold was heated to 120 F. The Example 48and found to require substantially more force resulting test specimenshad a 30% higher fiexural moduto overcome the tire cord-rubber adhesionthan was relu at 1% train and 15% more fiex ral strength after quired inthe case of control specimens not treated with exposure to boiling waterfor 72 hours than control moldthe azidosilane. ings made the same wayusing untreated glass beads.

EXAMPLE 50 EXAMPLE 53 This example shows the bonding of polyester fabricto silicone rubber using an azidosilane eompound This example shows theuse of an azidosilane compound Woven poly(ethylene terephthalate) fabricweighing 4 to 5126 glass ounces per square yard was dipped into a 24%solution of An aqueous sohmoh or by Welght q 2 m 3 [3 (t i th il l) 1azide silyl)ethylbenzenesulfonyl azide and 0.25% by weight formate inmethylene chloride, air dried, and then baked WaPer Soluble P Y resrhihavrhg an ePexrde equrvaleht in an oven f 1 hour at a temperature ofweight of 117, was applied to continuous rovings of elec- The thustreated fabric was plyed with 0.04 inch sheets meal, grass fibers asthey r formed at the grass drawlhg of silica filled, vinyl substitutedsilicon rubber, containing bushmg- The thu SlZed fovlngs were taken P011 a P L 0.5% by weight of benzoyl peroxide, forming a sandwichbakedfor hhrrhres e a temperature of frrrd like structure having polyesterfabric on the top and then chePPed h meh h The ehoPPed revhrgs bottomwith two sheets of silicon rubber in between. The W blended Wrth theerystahrhe Polypropylene deserrhed resulting structure was placed in arubber press, equipped Exarhpre 52 to Pr h a glese level P 30% Y w gwith spacers to hold the plates 0.072 inch apart. The The {nurture fasfed 1nt o a reciprocating screw in ection structure was then cured forminutes under pressure 40 {nehhhg meehrhe malhtarhed at zehe at atemperature of 110 F. The resulting laminate was 111 Zone 2, at thehozzle h the mold heated to tested to determine the force required toseparate the The VI/2 by by 5 rheh speerrhehe were tested and fabricfrom the rubber. In T-peel tests carried out at 2 rohhh to have ahexhrel strengthpf 45,000 control inches per minute the rubber failedrather than separating SPeerrnehS not treated Wrth the aFIdOShaheeempehhd e from the fabric (requiring a load of 4s lbs./il1.). -A con-45 a fiexurel Strength of 9,000 P- addltwn w the trol sample not treatedwith the azidosilane separated rerehee m etrehgth the treated revrhgs we h easrer f the rubber at about51bS /in to handle in that theymaintained their integrity to a EXAMPLE 51 much greater extent than theuntreated rovings. This example shows the bonding of polyester fabric toEXAMPLES 54 and 55 silicone rubber using an azidosilane compound. Theseexamples show the bonding of polymers to glass Woven poly(ethyleneterephthalate) fabric weighing 4 cloth which has been treated with anazidosilane comounces per square yard was dipped into a 22% solutionpound. of 2 (trimethoxysilyl)ethylbenzenesulfonyl azide in Strips of theglass cloth described in Example 18 were methylene chloride, air dried,and then baked in an air 55 immersed ina 0.37% by weight solution ofZ-(trimethoxyoven for 1 hour at a temperature of 177 C. The fabricsilyl)ethylbenzenesulfonyl azide in methylene chloride, was then dippedintoa 5% solution of vinyltriethoxysilane drained, and hung to dry. Theresulting treated glass in tetrachloroethylene, air dried, and baked inan air cloth was used to prepare 12 ply laminates with 2 dilferent ovenfor 20 minutes at a temperature of 150 F. The polymers as described inExample 18. Control samples thus treated fabric was plyed with 0.04 inchsheets of were prepared exactly as described above except the glasssilica filled vinyl substituted silicon rubber, containing cloth was notfirst treated with the azidosilane compound. 0.5% by weight of benzoylperoxide, forming a sandwich- Samples of the treated and controllaminates were tested like structure, cured and tested as described inExample as described in Examples 19-30. The polymers used and 50. InT-peel tests the rubber failed rather than separating the results of thetests are tabulated below:

72 hour boil fiexural Dry flexural properties properties Strength,Modulus, Strength, Modulus, Example Polymer p.s.i. p.s.i. (10 p.s.i.p.s.i. 10

54 Polyethylene 35, 500 2. 2 28, 400 2. 2 Control 11, 9 1. 5 7, 400 0. 855 Polybutene-l 24,150 1.6 10,600 1.2 Control 11,000 1.5 ,000 1.0

1 High density, having a specific gravity of 0.952 g./cc. and a meltindex of 4.6 g./10 min.

1 Isotactic,

I claim:

1. An article of manufacture comprising a material selected from thegroup consisting of siliceous materials, metals, metal oxides andpolymers treated with a nitrogen containing silane compound having theformula where R is an organic radical; X is a radical selected from thegroup consisting of halo, hydroxy, alkoxy, aryloxy, organo oxycarbonyl,azido, amine and amide radicals; T is a radical selected from the groupconsisting of alkyl, cycloalkyl, aryl, alkaryl, and aralkyl radicals; ais an integer from 1 to 3; b is an integer from to 2; c is an integerfrom 1 to d is an integer from 1 to 3; and a+b+d equals 4; and Z is aradical selected from the group consisting of where R is a radicalselected from the group consisting of hydrogen, alkyl, cycloalkyl, aryland COOR" radicals; where R" is a radical selected from the groupconsisting of alkyl, cycloalkyl and aryl radicals.

2. The article of claim 1 wherein the material is glass.

3. The article of claim 1 wherein the material is metal.

4. The article of claim 1 wherein the material is polymer.

5. An article of manufacture comprising a substrate primed with apolymer and a nitrogen containing silane compound having the formulawhere R is an organic radical; X is a radical selected from the groupconsisting of halo, hydroxy, alkoxy, aryloxy, organo oxycarbonyl, azido,amine and amide radicals; T is a radical selected from the groupconsisting of alkyl, cycloalkyl, aryl, alkaryl and aralkyl radicals; ais an integer from 1 to 3; b is an integer from 0 to 2; c is an integerfrom 1 to 10; d is an integer from 1 to 3; and a+b+d equals 4; and Z isa radical selected from the group consisting of II E o-c- N1, 00m, andSOzNa where R is a radical selected from the group consisting ofhydrogen, alkyl, cycloalkyl, aryl and COOR" radicals; where R is aradical selected from the group consisting of alkyl, cycloalkyl and arylradicals, said substrate being selected from the group consisting ofsiliceous materials, metal, metal oxide and other polymers.

6. The article of claim 5 wherein the substrate is glass.

7. The article of claim 5 wherein the substrate is metal.

8. The article of claim 5 wherein the substrate is another polymer.

9. A process of improving the adhesion of a polymer to a substrateselected from the group consisting of siliceous material, metal, metaloxide and other polymer substrates which comprises heating the substrateat an elevated temperature with the said polymer and a nitrogencontaining silane compound having the formula Where R is an organicradical; X is a radical selected from the group consisting of halo,hydroxy, alkoxy, aryloxy,

organo oxycarbonyl, azide, amine and amide radicals; T is a radicalselected from the group consisting of alkyl, cycloalkyl, aryl, alkaryland aralkyl radicals; a is an integer from 1 to 3; b is an integer from0 to 2; c is an integer from 1 to 10; d is an integer from 1 to 3; anda+b+d equals 4; and Z is a radical selected from the group consisting ofo R 0 II l II -C N2, -0CNs, and SO2NI where R is a radical selected fromthe group consisting of hydrogen, alkyl, cycloalkyl, aryl and COOR"radicals; where R" is a radical selected from the group consisting ofalkyl, cycloalkyl and aryl radicals.

10. The process of claim 9 wherein the substrate is first contacted withthe silane compound.

11. The process of claim 9 wherein the polymer and silane compound areprereacted.

12. The process of claim 9 wherein the polymer is a polyolefin.

13. The process of claim 9 wherein the polymer is a polyester.

14. An article of manufacture comprising a polymer bonded to a substratethrough a nitrogen containing silane compound having the formula where Ris an organic radical; X is a radical selected from the group consistingof halo, hydroxy, alkoxy, aryloxy, organo oxycarbonyl, azido, amine andamide radicals; T is a radical selected from the group consisting ofalkyl, cycloalkyl, aryl, alkaryl, and aralkyl radicals; a is an integerfrom 1 to 3; b is an integer from 0 to 2; c is an integer from 1 to 10;d is an integer from 1 to 3; and a+b+d equals 4; and Z is a radicalselected from the group consisting of where R is a radical selected fromthe group consisting of hydrogen, alkyl, cycloalkyl, aryl and -COOR"radicals; where R" is a radical selected from the group consisting ofalkyl, cycloalkyl and aryl radicals, said substrate being selected fromthe group consisting of siliceous material, metal, metal oxide and otherpolymer substrates.

15. The article of claim 14 wherein the polymer is bonded to glass.

16. The article of claim 14 wherein the polymer is bonded to metal.

17. The article of claim 14 wherein the polymer is a polyolefin.

18. The article of claim 14 wherein the polymer is a polyester.

References Cited UNITED STATES PATENTS 2,927,839 3/ 1960 Bailey et al.8-8 2,998,406 8/1961 Bailey et a1. 8-8 3,558,669 l/1971 Breslow 2603493,616,199 10/1971 Breslow 260349 WILLIAM D. MARTIN, Primary Examiner D.COHEN, Assistant Examiner US. Cl. X.R.

11776 T, S, 124 F, 121, 126 GS, GN, 135.1, 132 BS, 138.8 E, P; 260349,448.2 B, N, 141

